• Journal of Korean Society of Environmental Engineers
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• v.28 no.6
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• pp.620-625
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• 2006

In this investigation, an ICP-DRC/MS method to measure arsenic with ultra-trace concentration without any interference by the compounds such as $^{40}Ar^{35}Cl^+\;and\;^{40}Ca^{35}Cl^+$, which disturb the precise measurement of arsonic was described. Thus, the oxgen was introduced into the dynamic reaction cell as reaction gas and reacted with arsenic ion created in plasma gas, $AsO^+$ was formed and detected with m/z of 91 by ICP-MS. It resulted in better detection limit than the old method with m/z of 75($As^+$). The optimum condition for oxygen supply as the reaction gas was 0.5 mL/min. The analytical features of the method are as follows: detection limit of $0.02{\mu}g/L$, precision(RSD) of 3.4%, and recovery of 96%. Arsenic in the water samples from the tributary streams to the Han River and the main stream of Paldang were analyzed with this method to identify the characteristics in its distribution. The concentration of As ranged from 0.53 to $1.26{\mu}g/L$. We could measure As with very low concentration, less than $1.0{\mu}g/L$, with excellent reproducibility. The method developed is expected to be applied to analyze As of the samples from sea water, food, and domestic and industrial waste water which have high concentration of Cl and/or Ca.

• Analytical Science and Technology
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• v.16 no.1
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• pp.82-89
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• 2003

Isotope dilution mass spectrometry (IDMS) was applied to the determination of Ni, Cr, Mo in low alloy steel reference materials. The Mo isotope ratio measurement was performed by dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP/MS) using ammonia as a reaction cell gas. In the case of Ni and Cr measurement, all data were obtained at medium resolution mode (m/${\Delta}m=3000$) of double focusing sector field high resolution inductively coupled plasma mass spectrometry (HR-ICP/MS). For the method validation of the technique was assessed using the certified reference materials such as NIST SRM 361, NIST SRM 362, NIST SRM 363, NIST SRM 364, NIST SRM 36b. This method was applied to the determination of Ni, Cr and Mo in low alloy steel sample (CCQM-P25) provided by NMIJ for international comparison study.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.6
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• pp.621-627
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• 2008

In this study, a technique of speciation and determination of the trace inorganic arsenic(As(III) and As(V)) in water sample using HPLC-DRC-ICP-MS has been developed. Isocratic mobile phase of 10 mM ammonium nitrate and 10 mM ammonium phosphate monobasic was used and methanol(5 v/v%) was used as flushing solvent. Selection of the best flow rate of reaction gas, O$_2$, and optimization of the parameters such as pH and flow rate of mobile phase, and injection volume of sample for the separation and detection of arsenic species were carried out. The oxygen flow rate of 0.5 mL/min, pH of 9.4 and flow rate of 1.5 mL/min of mobile phase, and injection volume of sample of 100 $\mu$L were found to be the best parameters for the speciation and determination of arsenic species. The analytical features of the method were detection limit 0.10 and 0.08 $\mu$g/L, precision(RSD) 4.3% and 3.6%, and recovery 95.2% and 96.4% for As(III) and As(V), respectively. Analysis time was 4 minutes per sample. Linear calibration graphs with r$^2$ = 0.998 were obtained for both As(III) and As(V). Speciation analysis of arsenic species in the raw water samples collected from the tributary streams to Han River and main stream of Paldnag were performed by the proposed method. The concentrations of As(III) ranged from 0.10 to 0.22 $\mu$g/L and As(V) concentrations ranged from 0.44 to 1.19 $\mu$g/L, and 93.5% of total arsenic was found to be As(V).

• Analytical Science and Technology
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• v.29 no.5
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• pp.234-241
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• 2016

The approach presented in this article refers to the bioanalytical method validation for the detection and quantitative determination of arsenic species including arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) in dog plasma by high-performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP/MS). The arsenic species were separated using an agilent As speciation column by a mobile phase of 2 mM sodium phosphate monobasic, 0.2 mM ethylenediaminetetraacetic acid disodium salt dehydrate, 10 mM sodium acetate, 3 mM sodium nitrate and 1 % ethyl alcohol at pH 11 (adjusted with 1M NaOH). The method validation experiment was obtained selectivity, linearity, accuracy, precision, matrix effect, recovery, system suitability, dilution integrity and various stabilities. All calibration curves showed good linearity (R²>0.999) within test ranges. The lower limit of quantitation (LLOQ) was 5 ng/mL for As(III), As(V) and DMA, and 20 ng/mL for MMA. The system suitability and dilution values were within 6.5 % and 7.7 %. Subsequently, the developed and validated HPLC-ICP/MS method was also successfully applied to determine the arsenic speciation in dog plasma samples, and the recoveries for the spiked samples were in the range of 91.5–102.2 %. Therefore, this method could be applied to the evaluation of arsenic exposure, health effect assessment and other bio-monitoring studies in biological samples.

• Analytical Science and Technology
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• v.21 no.4
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• pp.316-325
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• 2008

An inductively coupled plasma mass spectrometry (ICP-MS) instrument equipped with flow injection-hydride generation system was used for the determination of trace arsenic in seawater sample. The accuracy in this method was verified by the analysis of certified reference materials (CRM) of seawater (CASS-4, NASS-5). The analytical results agreed with certified value within the range of uncertainty. The expanded uncertainties for CASS-4 and NASS-5 in this experiment were ranged from 6.2% to 6.8% obtained from repeated analyses of the CRMs (n=5). The detection limit of $As^+$ (m/z=74.9216) in this method was confirmed about 0.01 ug/kg. Linearity obtained from calibration curve of arsenic was excellent ($R^2=1$). The detection at $As^+$ (m/z=74.9216) and $AsO^+$ (m/z=90.9165) by using oxygen reaction gas in DRC mode was compared. Sensitivity at $AsO^+$ (m/z=90.9165) was decreased about 25-fold, but the analytical results are the same that at $As^+$ (m/z=74.9216).

• Journal of Korean Society of Environmental Engineers
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• v.27 no.6
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• pp.590-598
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• 2005

An adequate method to identify chromium separation, Cr(III) and Cr(VI), in water samples were studied by using High Performance Liquid Chromatography(HPLC) coupled with Inductively Coupled Plasma Mass Spectometer(ICP-MS) equipped with Dynamic Reaction Cell(DRC). The characteristic distribution of Cr(III) and Cr(VI) in the raw water taken at the six water intake stations in Seoul, was analyzed by the method developed by the authors. The chromium species separated by HPLC was isocratically conducted by using tetrabutylammonium phosphate monobasic(1.0 mM TBAP), ethylenediaminetetraacetic acid(0.6 mM EDTA) and 2% v/v methanol as the mobile phase. 5% v/v methanol was used as flushing solvent. A reactive ammonia($NH_3$) gas was used to eliminate the potential interference of $ArC^+$. Several Parameters such as solvent ratio, pH, flow rate and sample injection volume were optimized for the successful separation and reproducibility. Although it has been reported thai the separation sensitivity of Cr(III) is superior to that of Cr(VI), the authors observed Cr(VI) was more sensitive than Cr(III) when ammonia($NH_3$) gas was used as the reaction gas. It took less than 3 minutes to analyze chromium species with this method and the estimated detection limits were $0.061\;{\mu}g/L$ for Cr(III) and $0.052\;{\mu}g/L$, for Cr(VI). According to the results from the analysis on chromium species in the raw water of the six intake stations, the concentrations of Cr(III) ranged from 0.048 to $0.064\;{\mu}g/L$(ave. $0.054\;{\mu}g/L$) while that of Cr(VI) ranged from 0.014 to $0.023\;{\mu}g/L$(ave. $0.019\;{\mu}g/L$). Recovery ratio was very high($90.1{\sim}94.1%$). There were two or three times more Cr(III) than Cr(VI) in the raw water.

• Analytical Science and Technology
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• v.15 no.5
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• pp.417-426
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• 2002

Inductively Coupled Plasma Dynamic Reaction Cell Quadrupole Mass Spectrometry (ICP-DRC-QMS) was characterized for the detection of the six naturally occurring calcium isotopes. The effect of the operating conditions of the DRC system was studied to get the best signal-to-noise ratio. This experiment shows that the potentially interfering ions such as $Ar^+$, ${CO_2}^+$, ${NO_2}^+$, $CNO^+$ at the calcium masses m/z 40, 42, 43, 44 and 48 were removed by flowing $NH_3$ gas at the rate of 0.7 mL/min $NH_3$ as reactive cell gas in the DRC with a RPq value (rejection parameter) of 0.6. The limits of detection for $^{40}Ca$, $^{42}Ca$, $^{43}Ca$, $^{44}Ca$, and $^{48}Ca$ were 1, 29, 169, 34, and 15 pg/mL, respectively. This method was applied to the determination of calcium in synthetic food digest samples (CCQM-P13) provided by LGC for international comparison. The isotope dilution method was used for the determination of calcium in the samples. The uncertainty evaluation was performed according to the ISO/GUM and EURACHEM guidelines. The determined mean concentration and its expanded uncertainty of calcium was ($66.4{\pm}1.2$) mg/kg. In order to assess our method, two reference samples, Riverine Water reference sample (NRCC SLRS-3) and Trace Elements in Water reference sample (NIST SRM 1643d), were analyzed.

• Journal of the Korean Society for Marine Environment & Energy
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• v.17 no.4
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• pp.257-267
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• 2014

The distributions of trace metals in the East Sea were investigated during the R/V Lavrentyev cruise (July 2009) in which four transects from Russia shore to South were conducted to collect 25 surface water samples. The total dissolved concentrations of Cu and Ni were measured using ICP-MS, DRC-e. In the coastal area, their concentrations of Russia shore (Cu, 1.51; Ni, 1.82 nM) were 1.9 times for Cu and 2.0 times for Ni lower than Korea shore (Cu, 2.87; Ni, 3.71 nM). In the subregion, their concentrations of Warm region (Cu, 3.03; Ni, 2.28 nM) were higher for Cu than Cold region (Cu, 2.04; Ni, 2.28 nM). The distributions of Cu and Ni concentrations were divided by lowest level at $10^{\circ}C$ of water temperature. In this study period, the surface water temperatures of Russia shore and Japan basin were lower than $10^{\circ}C$ and them of Ulleung basin and Sakhalin shore were higher. Below $10^{\circ}C$, Cu and Ni concentrations increased when surface water temperatures decreased. Above $10^{\circ}C$, their concentrations increased with temperature, which showed highest concentrations in the Ulleung basin, directly influenced by flux from East Korean Warm Current. By comparing with other sea areas (Western Mediterranean, Atlantic), Cu concentrations in the East Sea were a little higher and Ni concentrations were lower. Particularly as the level of Cu in the offshore in the Ulleung basin were higher than in the coastal area, We can suggest that the atmospheric flux of Cu is relatively important in this area.

• Journal of the Korean Society for Marine Environment & Energy
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• v.18 no.2
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• pp.64-73
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• 2015

The distributions of Pb and Cd concentrations in the surface seawater of the East Sea were investigated during the R/V Lavrentyev cruise (July 2009) in which four transects from Russia shore to South were conducted to collect 26 surface water samples. The total dissolved concentrations of Pb and Cd were measured using ICP-MS (Perkin Elmer, DRC-e). In the coastal area, their concentrations of Russia shore (Pb, 0.08; Cd, 0.10 nM) were comparable for Cd but on the other hand, 6 times lower for Pb than Korea shore (Pb, 0.49; Cd, 0.11 nM). In the subregion, their concentrations of Warm region (Pb, 0.22; Cd, 0.01 nM) were about 1.7 times higher for Pb but 0.4 lower for Cd than Cold region (Pb, 0.13; Cd, 0.14 nM). The distributions of Pb and Cd concentrations were divided by lowest level at $10^{\circ}C$ of water temperature. Below $10^{\circ}C$, Pb and Cd concentrations increased when surface water temperatures decreased. Above $10^{\circ}C$, their concentrations increased with temperature, which showed highest concentrations in the Ulleung basin, directly influenced by flux from East Korean Warm Current and neighboring countrys (Korea and Japan). Specially, in the case of Pb, the concentrations decrease remarkablely with temperatures decrease from D10 directly influenced by flux from East Korean Warm Current, which shows highest Pb level. By comparing with other sea areas (Western Mediterranean, East Pacific), Pb concentrations in the East Sea were a little higher. The influence of East Korean Warm Current and neighboring countrys (Korea and Japan) may be relatively important. Therefore, the distribution of Cd may primarily be influenced by mixing of different water masses while the distribution of Pb may mainly be influenced by flux from East Korean Warm Current and atmospheric inputs. River inputs and interaction with particulate materials may also some roles for the distribution of these elements.